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###                                                                        ###
###           Electronic papers (Acta Crystallographica Section C)         ###
###                                                                        ###
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# This paper is published electronically. It meets the data-validation       #
# criteria for publication in Acta Crystallographica Section C.              #
# The submission has been checked by a Section C Co-editor though the text   #
# in _publ_section_comments is the responsibility of the authors.            #
#                                                                            #
# Electronic papers are listed in the printed contents pages of an issue of  #
# Acta Crystallographica Section C within two months of acceptance and are   #
# available by email and via the online contents pages for that issue.       #
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data_global
_audit_creation_method     'manual editing of SHELXL created .cif file'
_journal_data_validation_number     IUC0000047
_journal_date_recd_electronic     2000-01-17
_journal_date_accepted     2000-02-11
_journal_name_full     'Acta Crystallographica, Section C'
_journal_year     2000
_journal_volume     56
_journal_issue      3
_journal_page_first     e88
_journal_page_last     e89
_journal_paper_category     CM
_publ_contact_author_name     'Dr Prakas R Maulik'
_publ_contact_author_address
; Division of Membrane Biology
  Central Drug Research Institute
  Chattar Manzil, Post Box No. 173
  Lucknow 226 001
  India
;
_publ_contact_author_email     root@cscdri.ren.nic.in
_publ_contact_author_fax     '91(0522)223405'
_publ_section_title
;
A highly functionalized ferrocenylpyrazolo[2,3-a]pyridine
;
_publ_section_title_footnote
;
CDRI Communication No. 5997.
;
loop_
    _publ_author_name
    _publ_author_address
    'Sarkhel, Sanjay'
;
Division of Membrane Biology
Central Drug Research Institute
Lucknow 226 001
India
;
    'Srivastava, Prativa'
;
Medicinal Chemistry Division
Central Drug Research Institute
Lucknow 226 001
India
;
    'Ram, Vishnu J.'
;
Medicinal Chemistry Division
Central Drug Research Institute
Lucknow 226 001
India
;
    'Maulik, Prakas R.'
;
Division of Membrane Biology
Central Drug Research Institute
Lucknow 226 001
India
;
    'Broder, Charlotte K.'
;
Department of Chemistry
University of Durham
Durham DH1 3LE
England
;
    'Howard, Judith A. K.'
;
Department of Chemistry
University of Durham
Durham DH1 3LE
England
;
_publ_section_synopsis
;
The crystal structure analysis of the substituted ferrocene complex
2-[2-(4-bromophenyl)-4-cyano-5-ferrocenylpyrazolo[2,3-a]pyridin-7-yl]-
acetonitrile shows that the pyrazolo-pyridine ring system, the bromophenyl
ring and the cyclopentadiene ring are nearly planar.
;
_publ_section_abstract
;
The crystal structure of
[2-(4-bromophenyl)-4-cyano-5-ferrocenylpyrazolo[2,3-a]pyridin-7-yl]-
acetonitrile, C₂₆H₁₇N₄FeBr or [Fe(C₅H₅)(C₂₁H₁₂BrN₄)],
shows that the pyrazolopyridine ring system (PP), the bromophenyl ring
(BP) and the cyclopentadiene ring (Cp) are nearly planar. The PP ring
system is twisted out of the plane of the BP and Cp rings by about 20°.
;
_publ_section_comment
;
In view of the recent growing interest in the field of asymmetric
synthesis, ferrocene and its derivatives occupy an important
place in synthetic and materials chemistry due to their unique
non-linear optical, liquid and crystalline and ferromagnetic
properties (Hayashi, 1995). The 1,2- and 1,3-disubstituted
ferrocene derivatives, having planar chirality, are suitable
chiral reference systems for asymmetric induced synthesis
(Marquarding et al., 1970). The unique
properties of these compounds encouraged the synthesis of ferrocene
derivatives with highly functionalized ring systems directly linked
to one of the cyclopentadiene moieties. These compounds do not
exhibit optical activity due to lack of restricted rotation. The
title compound was synthesized following a procedure reported
earlier (Nath et al., 1998). The structure
of the title compound, (I), was assigned by IR, NMR and mass
spectra, but the conformation of the ferrocene moiety with respect to
the heterocyclic ring was of particular interest and prompted us to
undertake the present X-ray diffraction study.
The title molecule contains one pyrazolo[2,3-a]pyridine
fused-ring system (PP), one bromo-phenyl ring (BP) and one ferrocenyl
moiety.
The two individual rings [inclined to each other by an angle 1.9(2)°]
in the
PP system and the BP ring are planar [the deviations of the atoms from the
least-squares planes are within the range -0.012(3)--0.006(3)Å]. The -CN
group at C12 lies slightly out of the PP ring system [torsion angle
C6---C7---C12---C13 -7.2(6)°]. The cyclopentadiene rings of the ferrocene
moiety
are essentually elipsed [the mean value of the five torsion angles
CnA---CgA---CgB---CnB (where n = 1--5, and CgA and CgB are the Cp ring
centroids) is 4.9(6)°]. The Cp rings are parallel [dihedral angle 2.4(3)°]
and each lies equidistant [1.65(1)Å] from the Fe atom. Both the
BP and Cp rings adopt a twist conformation with respect to the PP
ring system [torsion angle N1---C2---C1'---C6' -17.8(6)°
and C6---C5---C1A---C5A 20.6(6)°]. There are no short contacts or
intermolecular stacking interactions in the lattice.
;
_publ_section_acknowledgements
;
SS and PS thank CSIR, India, for a Senior Research Fellowship.
CKB and JAKH thank the EPSRC for their support.
;
_publ_section_references
;
Gabe, E. J., Le Page, Y., Charland, J.-P., Lee, F. L. & White, P. S.
(1989). J. Appl. Cryst. 22, 384-387.
Hayashi, T. (1995). Ferrocenes, edited by A. Togni. Weinheim: VCH.
Marquarding, D., Klusacek, H., Gokel, G., Hoffmann, P. & Ugi, I.
(1970). J. Am. Chem. Soc. 92, 5389-5393.
Nath, M., Srivastava, P., Goel, A. & Ram, V. J. (1998). Eur. J. Org
Chem. pp. 2083-2088.
Sheldrick, G. M. (1990). Acta Cryst. A46, 467-473.
Sheldrick, G. M. (1993). SHELXL93. University of Göttingen, Germany.
Sheldrick, G. M. (1994). SHELXTL. Release 4.1 Siemens Analytical X-ray
Instruments Inc., Madision, Wisconsin, USA.
Bruker (1998). SMART and SAINT. Bruker AXS Inc, Madison, Wisconsin,
USA.
;
_publ_section_exptl_prep
;
The synthesis of (I) was carried out by the reaction of
3-cyano-6-ferrocenyl-4-methylthio-2H-pyran-2-one with
5-(4-bromophenyl)-3-cyanomethyl-1H-pyrazole in a 1:1 molar ratio in dry
DMF in the presence of KOH (Nath et al., 1998). Diffraction quality
crystals were grown by slow evaporation from a mixture of
dichloromethane and hexane at room temperature.
;
_publ_section_exptl_refinement
;
All H atoms were placed in geometrically idealized positions and allowed
to ride on their parent atoms, to which each was bonded for the final
cycles of refinement. Nine reflections [most disagreeable, Δ(F²)/σ > 5.0]
were suppressed during the last cycles of refinement.
;
data_I
_chemical_name_systematic
;
2-[(4-Bromophenyl)-4-cyano-5-ferrocenylpyrazolo[1,5-a]pyridin-7yl]
acetonitrile
;
_chemical_name_common     Pyrazolo[1,5-a]pyridine
_chemical_formula_moiety     ?
_chemical_formula_sum     'C26 H17 Br Fe N4'
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_formula_iupac     '[Fe (C5 H5 )(C21 H12 Br N4)]'
_chemical_formula_weight     521.20
_chemical_melting_point     230
_symmetry_cell_setting     triclinic
_symmetry_space_group_name_H-M     'P -1'
loop_
    _symmetry_equiv_pos_as_xyz
    'x, y, z'
    '-x, -y, -z'
_cell_length_a     7.96080(10)
_cell_length_b     10.68440(10)
_cell_length_c     12.8215(3)
_cell_angle_alpha     93.5770(10)
_cell_angle_beta     97.7370(10)
_cell_angle_gamma     99.0460(10)
_cell_volume     1063.28(3)
_cell_formula_units_Z     2
_cell_measurement_reflns_used     509
_cell_measurement_theta_min     2.99
_cell_measurement_theta_max     25.55
_cell_measurement_temperature     150(2)
_exptl_crystal_description     plate
_exptl_crystal_colour     red
_exptl_crystal_size_max      .25
_exptl_crystal_size_mid      .15
_exptl_crystal_size_min      .06
_exptl_crystal_density_diffrn     1.628
_exptl_crystal_density_meas     ?
_exptl_crystal_density_method     'not measured'
_exptl_crystal_F_000     524
_exptl_absorpt_coefficient_mu     2.610
_exptl_absorpt_correction_type     '\y scan'
_exptl_absorpt_process_details     '(XPREP; Sheldrick, 1994)'
_exptl_absorpt_correction_T_min      .606
_exptl_absorpt_correction_T_max      .855
_exptl_special_details
;
?
;
_diffrn_ambient_temperature     150(2)
_diffrn_radiation_type     MoK\a
_diffrn_radiation_wavelength      .71073
_diffrn_radiation_source     'fine-focus sealed tube'
_diffrn_radiation_monochromator     graphite
_diffrn_measurement_device     'Bruker SMARTCCD'
_diffrn_measurement_method     ω
_diffrn_reflns_number     7790
_diffrn_reflns_av_R_equivalents      .0403
_diffrn_reflns_av_sigmaI/netI      .0475
_diffrn_reflns_theta_min     1.61
_diffrn_reflns_theta_max     27.49
_diffrn_reflns_limit_h_min     -10
_diffrn_reflns_limit_h_max     9
_diffrn_reflns_limit_k_min     -13
_diffrn_reflns_limit_k_max     10
_diffrn_reflns_limit_l_min     -16
_diffrn_reflns_limit_l_max     16
_diffrn_standards_number     .
_diffrn_standards_interval_count     .
_diffrn_standards_interval_time     .
_diffrn_standards_decay_%     0
_reflns_number_total     4823
_reflns_number_observed     3953
_reflns_observed_criterion     I>2\s(I)
_refine_ls_structure_factor_coef     Fsqd
_refine_ls_matrix_type     full
_refine_ls_R_factor_all      .068
_refine_ls_R_factor_obs      .048
_refine_ls_wR_factor_all      .140
_refine_ls_wR_factor_obs      .106
_refine_ls_goodness_of_fit_all     1.028
_refine_ls_goodness_of_fit_obs      .933
_refine_ls_restrained_S_all     1.114
_refine_ls_restrained_S_obs      .933
_refine_ls_number_reflns     4783
_refine_ls_number_parameters     289
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment     constr
_refine_ls_weighting_scheme
     'calc w = 1/[\s^2^(Fo^2^)+(0.0381P)^2^+4.8638P] where P = (Fo^2^+2Fc^2^)/3'
_refine_ls_shift/esd_max      -.001
_refine_ls_shift/esd_mean      .000
_refine_diff_density_max      .457
_refine_diff_density_min      -.358
_refine_ls_extinction_method     none
_refine_ls_extinction_coef     ?
loop_
    _atom_type_symbol
    _atom_type_description
    _atom_type_scat_dispersion_real
    _atom_type_scat_dispersion_imag
    _atom_type_scat_source
    'C' 'C'  .0033  .0016
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'H' 'H'  .0000  .0000
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'N' 'N'  .0061  .0033
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'Fe' 'Fe'  .3463  .8444
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
    'Br' 'Br'  -.2901 2.4595
                         'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
_computing_data_collection     'SMART (Bruker, 1998)'
_computing_cell_refinement     'SMART'
_computing_data_reduction     'SAINT (Bruker, 1998)'
_computing_structure_solution     'SHELXS86 (Sheldrick, 1990)'
_computing_structure_refinement     'SHELXL93 (Sheldrick, 1993)'
_computing_molecular_graphics     'NRCVAX (Gabe et al., 1989)'
_computing_publication_material     'SHELXL93'
loop_
    _atom_site_label
    _atom_site_fract_x
    _atom_site_fract_y
    _atom_site_fract_z
    _atom_site_U_iso_or_equiv
    _atom_site_thermal_displace_type
    _atom_site_calc_flag
    _atom_site_refinement_flags
    _atom_site_occupancy
    _atom_site_disorder_group
    _atom_site_type_symbol
    Br  .44869(6)  .74199(5)  .35615(3)  .03315(14) Uani d . 1 . Br
    Fe 1.00953(8) 1.43332(6) 1.27215(5)  .0236(2) Uani d . 1 . Fe
    N1 1.0036(4) 1.0849(3)  .7807(3)  .0212(7) Uani d . 1 . N
    C2  .8354(5) 1.0328(4)  .7704(3)  .0227(8) Uani d . 1 . C
    C1'  .7432(5)  .9683(4)  .6690(3)  .0225(8) Uani d . 1 . C
    C2'  .5900(5)  .8835(4)  .6689(3)  .0265(9) Uani d . 1 . C
    H2'  .5473  .8709  .7321  .032 Uiso calc R 1 . H
    C3'  .5009(5)  .8177(4)  .5759(3)  .0274(9) Uani d . 1 . C
    H3'  .3985  .7621  .5761  .033 Uiso calc R 1 . H
    C4'  .5687(5)  .8370(4)  .4824(3)  .0253(9) Uani d . 1 . C
    C5'  .7189(5)  .9210(4)  .4792(3)  .0268(9) Uani d . 1 . C
    H5'  .7607  .9333  .4156  .032 Uiso calc R 1 . H
    C6'  .8064(5)  .9868(4)  .5733(3)  .0259(9) Uani d . 1 . C
    H6'  .9075 1.0435  .5724  .031 Uiso calc R 1 . H
    C3  .7656(5) 1.0495(4)  .8640(3)  .0211(8) Uani d . 1 . C
    H3  .6531 1.0217  .8749  .025 Uiso calc R 1 . H
    C4  .9184(5) 1.1670(4) 1.0441(3)  .0208(8) Uani d . 1 . C
    C5 1.0748(5) 1.2339(4) 1.0944(3)  .0223(8) Uani d . 1 . C
    C1A 1.1057(5) 1.2849(4) 1.2055(3)  .0221(8) Uani d . 1 . C
    C2A 1.0095(6) 1.2438(4) 1.2890(3)  .0279(9) Uani d . 1 . C
    H2A  .9129 1.1806 1.2816  .034 Uiso calc R 1 . H
    C3A 1.0890(6) 1.3172(4) 1.3849(3)  .0317(10) Uani d . 1 . C
    H3A 1.0536 1.3095 1.4507  .038 Uiso calc R 1 . H
    C4A 1.2314(6) 1.4041(4) 1.3624(3)  .0288(9) Uani d . 1 . C
    H4A 1.3044 1.4635 1.4109  .035 Uiso calc R 1 . H
    C5A 1.2430(5) 1.3848(4) 1.2530(3)  .0245(8) Uani d . 1 . C
    H5A 1.3254 1.4291 1.2179  .029 Uiso calc R 1 . H
    C1B  .8700(7) 1.5064(5) 1.1520(4)  .0410(12) Uani d . 1 . C
    H1B  .8555 1.4791 1.0806  .049 Uiso calc R 1 . H
    C2B  .7626(6) 1.4611(5) 1.2255(5)  .0456(14) Uani d . 1 . C
    H2B  .6657 1.3982 1.2109  .055 Uiso calc R 1 . H
    C3B  .8282(7) 1.5283(5) 1.3255(5)  .0420(12) Uani d . 1 . C
    H3B  .7822 1.5173 1.3878  .050 Uiso calc R 1 . H
    C4B  .9764(6) 1.6150(4) 1.3129(4)  .0333(10) Uani d . 1 . C
    H4B 1.0443 1.6716 1.3657  .040 Uiso calc R 1 . H
    C5B 1.0040(6) 1.6009(5) 1.2063(4)  .0344(10) Uani d . 1 . C
    H5B 1.0937 1.6455 1.1770  .041 Uiso calc R 1 . H
    C6 1.2138(5) 1.2519(4) 1.0331(3)  .0219(8) Uani d . 1 . C
    H6 1.3193 1.2980 1.0646  .026 Uiso calc R 1 . H
    C7 1.1965(5) 1.2038(4)  .9302(3)  .0218(8) Uani d . 1 . C
    N8 1.0405(4) 1.1352(3)  .8837(3)  .0198(7) Uani d . 1 . N
    C9  .8985(5) 1.1159(4)  .9364(3)  .0204(8) Uani d . 1 . C
    C10  .7638(6) 1.1435(4) 1.0915(3)  .0270(9) Uani d . 1 . C
    N11  .6341(5) 1.1199(5) 1.1207(3)  .0423(11) Uani d . 1 . N
    C12 1.3299(5) 1.2185(4)  .8572(3)  .0255(9) Uani d . 1 . C
    H12A 1.3596 1.1358  .8401  .031 Uiso calc R 1 . H
    H12B 1.2809 1.2487  .7920  .031 Uiso calc R 1 . H
    C13 1.4873(6) 1.3068(5)  .9018(3)  .0299(9) Uani d . 1 . C
    N14 1.6111(5) 1.3756(5)  .9303(3)  .0460(12) Uani d . 1 . N
_geom_special_details
;
All esds (except the esd in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix.  The cell esds are taken
into account individually in the estimation of esds in distances, angles
and torsion angles; correlations between esds in cell parameters are
only
used when they are defined by crystal symmetry.  An approximate
(isotropic)
treatment of cell esds is used for estimating esds involving l.s.
planes.
;
loop_
    _geom_bond_atom_site_label_1
    _geom_bond_atom_site_label_2
    _geom_bond_site_symmetry_2
    _geom_bond_distance
    _geom_bond_publ_flag
    Br C4' . 1.907(4) ?
    Fe C5B . 2.031(5) yes
    Fe C4B . 2.045(4) yes
    Fe C2B . 2.049(5) yes
    Fe C1A . 2.054(4) yes
    Fe C5A . 2.048(4) yes
    Fe C2A . 2.050(4) yes
    Fe C1B . 2.044(5) yes
    Fe C4A . 2.055(4) yes
    Fe C3B . 2.054(5) yes
    Fe C3A . 2.062(5) yes
    N1 C2 . 1.353(5) ?
    N1 N8 . 1.370(4) ?
    C2 C3 . 1.401(5) ?
    C2 C1' . 1.475(5) ?
    C1' C2' . 1.400(6) ?
    C1' C6' . 1.402(6) ?
    C2' C3' . 1.389(6) ?
    C2' H2' .  .93 ?
    C3' C4' . 1.394(6) ?
    C3' H3' .  .93 ?
    C4' C5' . 1.385(6) ?
    C5' C6' . 1.396(6) ?
    C5' H5' .  .93 ?
    C6' H6' .  .93 ?
    C3 C9 . 1.379(5) ?
    C3 H3 .  .93 ?
    C4 C5 . 1.387(6) ?
    C4 C9 . 1.432(5) ?
    C4 C10 . 1.439(6) ?
    C5 C6 . 1.436(6) ?
    C5 C1A . 1.468(5) ?
    C1A C5A . 1.441(6) ?
    C1A C2A . 1.449(6) ?
    C2A C3A . 1.428(6) ?
    C2A H2A .  .93 ?
    C3A C4A . 1.422(7) ?
    C3A H3A .  .93 ?
    C4A C5A . 1.423(6) ?
    C4A H4A .  .93 ?
    C5A H5A .  .93 ?
    C1B C2B . 1.413(8) ?
    C1B C5B . 1.419(7) ?
    C1B H1B .  .93 ?
    C2B C3B . 1.420(7) ?
    C2B H2B .  .93 ?
    C3B C4B . 1.415(7) ?
    C3B H3B .  .93 ?
    C4B C5B . 1.416(7) ?
    C4B H4B .  .93 ?
    C5B H5B .  .93 ?
    C6 C7 . 1.367(5) ?
    C6 H6 .  .93 ?
    C7 N8 . 1.377(5) ?
    C7 C12 . 1.503(5) ?
    N8 C9 . 1.388(5) ?
    C10 N11 . 1.142(6) ?
    C12 C13 . 1.468(6) ?
    C12 H12A .  .97 ?
    C12 H12B .  .97 ?
    C13 N14 . 1.134(6) ?
loop_
    _geom_angle_atom_site_label_1
    _geom_angle_atom_site_label_2
    _geom_angle_atom_site_label_3
    _geom_angle_site_symmetry_1
    _geom_angle_site_symmetry_3
    _geom_angle
    _geom_angle_publ_flag
    C5B Fe C4B . . 40.7(2) ?
    C5B Fe C2B . . 68.4(2) ?
    C4B Fe C2B . . 67.9(2) ?
    C5B Fe C1A . . 123.2(2) ?
    C4B Fe C1A . . 160.3(2) ?
    C2B Fe C1A . . 121.5(2) ?
    C5B Fe C5A . . 105.6(2) ?
    C4B Fe C5A . . 123.4(2) ?
    C2B Fe C5A . . 156.1(2) ?
    C1A Fe C5A . . 41.1(2) ?
    C5B Fe C2A . . 161.7(2) ?
    C4B Fe C2A . . 156.8(2) ?
    C2B Fe C2A . . 109.2(2) ?
    C1A Fe C2A . . 41.4(2) ?
    C5A Fe C2A . . 68.9(2) ?
    C5B Fe C1B . . 40.8(2) ?
    C4B Fe C1B . . 68.1(2) ?
    C2B Fe C1B . . 40.4(2) ?
    C1A Fe C1B . . 106.9(2) ?
    C5A Fe C1B . . 120.1(2) ?
    C2A Fe C1B . . 125.6(2) ?
    C5B Fe C4A . . 119.4(2) ?
    C4B Fe C4A . . 107.0(2) ?
    C2B Fe C4A . . 162.7(2) ?
    C1A Fe C4A . . 68.9(2) ?
    C5A Fe C4A . . 40.6(2) ?
    C2A Fe C4A . . 68.5(2) ?
    C1B Fe C4A . . 154.9(2) ?
    C5B Fe C3B . . 68.4(2) ?
    C4B Fe C3B . . 40.4(2) ?
    C2B Fe C3B . . 40.5(2) ?
    C1A Fe C3B . . 157.4(2) ?
    C5A Fe C3B . . 160.8(2) ?
    C2A Fe C3B . . 122.3(2) ?
    C1B Fe C3B . . 68.1(2) ?
    C4A Fe C3B . . 125.1(2) ?
    C5B Fe C3A . . 155.2(2) ?
    C4B Fe C3A . . 121.3(2) ?
    C2B Fe C3A . . 126.8(2) ?
    C1A Fe C3A . . 68.9(2) ?
    C5A Fe C3A . . 68.3(2) ?
    C2A Fe C3A . . 40.6(2) ?
    C1B Fe C3A . . 163.2(2) ?
    C4A Fe C3A . . 40.4(2) ?
    C3B Fe C3A . . 109.0(2) ?
    C2 N1 N8 . . 103.5(3) ?
    N1 C2 C3 . . 112.5(3) ?
    N1 C2 C1' . . 121.1(4) ?
    C3 C2 C1' . . 126.4(4) ?
    C2' C1' C6' . . 119.0(4) ?
    C2' C1' C2 . . 118.9(4) ?
    C6' C1' C2 . . 122.0(4) ?
    C3' C2' C1' . . 121.2(4) ?
    C3' C2' H2' . . 119.4(2) ?
    C1' C2' H2' . . 119.4(2) ?
    C2' C3' C4' . . 118.3(4) ?
    C2' C3' H3' . . 120.8(2) ?
    C4' C3' H3' . . 120.8(2) ?
    C5' C4' C3' . . 122.2(4) ?
    C5' C4' Br . . 119.9(3) ?
    C3' C4' Br . . 117.8(3) ?
    C4' C5' C6' . . 118.7(4) ?
    C4' C5' H5' . . 120.7(2) ?
    C6' C5' H5' . . 120.7(2) ?
    C5' C6' C1' . . 120.6(4) ?
    C5' C6' H6' . . 119.7(2) ?
    C1' C6' H6' . . 119.7(2) ?
    C9 C3 C2 . . 105.6(3) ?
    C9 C3 H3 . . 127.2(2) ?
    C2 C3 H3 . . 127.2(2) ?
    C5 C4 C9 . . 121.0(4) ?
    C5 C4 C10 . . 125.0(4) ?
    C9 C4 C10 . . 114.0(3) ?
    C4 C5 C6 . . 117.2(4) ?
    C4 C5 C1A . . 123.8(4) ?
    C6 C5 C1A . . 119.0(4) ?
    C5A C1A C2A . . 106.7(3) ?
    C5A C1A C5 . . 125.8(4) ?
    C2A C1A C5 . . 127.5(4) ?
    C5A C1A Fe . . 69.2(2) ?
    C2A C1A Fe . . 69.2(2) ?
    C5 C1A Fe . . 127.8(3) ?
    C3A C2A C1A . . 108.1(4) ?
    C3A C2A Fe . . 70.1(3) ?
    C1A C2A Fe . . 69.5(2) ?
    C3A C2A H2A . . 126.0(3) ?
    C1A C2A H2A . . 126.0(2) ?
    Fe C2A H2A . . 126.01(13) ?
    C4A C3A C2A . . 108.4(4) ?
    C4A C3A Fe . . 69.5(3) ?
    C2A C3A Fe . . 69.2(2) ?
    C4A C3A H3A . . 125.8(2) ?
    C2A C3A H3A . . 125.8(3) ?
    Fe C3A H3A . . 127.00(13) ?
    C5A C4A C3A . . 108.3(4) ?
    C5A C4A Fe . . 69.5(2) ?
    C3A C4A Fe . . 70.1(3) ?
    C5A C4A H4A . . 125.8(2) ?
    C3A C4A H4A . . 125.8(2) ?
    Fe C4A H4A . . 126.21(13) ?
    C4A C5A C1A . . 108.6(4) ?
    C4A C5A Fe . . 70.0(2) ?
    C1A C5A Fe . . 69.7(2) ?
    C4A C5A H5A . . 125.7(2) ?
    C1A C5A H5A . . 125.7(2) ?
    Fe C5A H5A . . 126.25(12) ?
    C2B C1B C5B . . 108.1(4) ?
    C2B C1B Fe . . 70.0(3) ?
    C5B C1B Fe . . 69.1(3) ?
    C2B C1B H1B . . 126.0(3) ?
    C5B C1B H1B . . 126.0(3) ?
    Fe C1B H1B . . 126.47(14) ?
    C3B C2B C1B . . 108.2(5) ?
    C3B C2B Fe . . 69.9(3) ?
    C1B C2B Fe . . 69.6(3) ?
    C3B C2B H2B . . 125.9(3) ?
    C1B C2B H2B . . 125.9(3) ?
    Fe C2B H2B . . 126.1(2) ?
    C4B C3B C2B . . 107.5(5) ?
    C4B C3B Fe . . 69.4(3) ?
    C2B C3B Fe . . 69.5(3) ?
    C4B C3B H3B . . 126.2(3) ?
    C2B C3B H3B . . 126.2(3) ?
    Fe C3B H3B . . 126.3(2) ?
    C3B C4B C5B . . 108.5(4) ?
    C3B C4B Fe . . 70.2(3) ?
    C5B C4B Fe . . 69.2(3) ?
    C3B C4B H4B . . 125.7(3) ?
    C5B C4B H4B . . 125.7(3) ?
    Fe C4B H4B . . 126.50(13) ?
    C4B C5B C1B . . 107.6(5) ?
    C4B C5B Fe . . 70.2(3) ?
    C1B C5B Fe . . 70.1(3) ?
    C4B C5B H5B . . 126.2(3) ?
    C1B C5B H5B . . 126.2(3) ?
    Fe C5B H5B . . 125.14(14) ?
    C7 C6 C5 . . 122.4(4) ?
    C7 C6 H6 . . 118.8(2) ?
    C5 C6 H6 . . 118.8(2) ?
    C6 C7 N8 . . 118.8(4) ?
    C6 C7 C12 . . 127.5(4) ?
    N8 C7 C12 . . 113.7(3) ?
    N1 N8 C7 . . 125.0(3) ?
    N1 N8 C9 . . 112.4(3) ?
    C7 N8 C9 . . 122.5(3) ?
    C3 C9 N8 . . 106.0(3) ?
    C3 C9 C4 . . 135.9(4) ?
    N8 C9 C4 . . 118.0(3) ?
    N11 C10 C4 . . 174.0(5) ?
    C13 C12 C7 . . 113.5(3) ?
    C13 C12 H12A . . 108.9(3) ?
    C7 C12 H12A . . 108.9(2) ?
    C13 C12 H12B . . 108.9(2) ?
    C7 C12 H12B . . 108.9(2) ?
    H12A C12 H12B . . 107.7 ?
    N14 C13 C12 . . 175.9(5) ?
loop_
    _geom_torsion_atom_site_label_1
    _geom_torsion_atom_site_label_2
    _geom_torsion_atom_site_label_3
    _geom_torsion_atom_site_label_4
    _geom_torsion_site_symmetry_1
    _geom_torsion_site_symmetry_2
    _geom_torsion_site_symmetry_3
    _geom_torsion_site_symmetry_4
    _geom_torsion
    _geom_torsion_publ_flag
    N8 N1 C2 C3 . . . .  .3(5) ?
    N8 N1 C2 C1' . . . . 179.5(4) ?
    N1 C2 C1' C2' . . . . 160.5(4) ?
    C3 C2 C1' C2' . . . . -20.4(6) ?
    N1 C2 C1' C6' . . . . -17.8(6) ?
    C3 C2 C1' C6' . . . . 161.3(4) ?
    C6' C1' C2' C3' . . . .  .2(6) ?
    C2 C1' C2' C3' . . . . -178.2(4) ?
    C1' C2' C3' C4' . . . .  .7(7) ?
    C2' C3' C4' C5' . . . . -1.3(7) ?
    C2' C3' C4' Br . . . . 178.0(3) ?
    C3' C4' C5' C6' . . . . 1.0(7) ?
    Br C4' C5' C6' . . . . -178.4(3) ?
    C4' C5' C6' C1' . . . .  .0(7) ?
    C2' C1' C6' C5' . . . .  -.5(6) ?
    C2 C1' C6' C5' . . . . 177.8(4) ?
    N1 C2 C3 C9 . . . .  .0(5) ?
    C1' C2 C3 C9 . . . . -179.2(4) ?
    C9 C4 C5 C6 . . . . 1.4(6) ?
    C10 C4 C5 C6 . . . . -177.7(4) ?
    C9 C4 C5 C1A . . . . -177.8(4) ?
    C10 C4 C5 C1A . . . . 3.1(7) ?
    C4 C5 C1A C5A . . . . -160.1(4) ?
    C6 C5 C1A C5A . . . . 20.6(6) ?
    C4 C5 C1A C2A . . . . 21.8(7) ?
    C6 C5 C1A C2A . . . . -157.4(4) ?
    C4 C5 C1A Fe . . . . -69.8(5) ?
    C6 C5 C1A Fe . . . . 110.9(4) ?
    C5B Fe C1A C5A . . . . 74.9(3) ?
    C4B Fe C1A C5A . . . . 44.5(6) ?
    C2B Fe C1A C5A . . . . 158.3(3) ?
    C2A Fe C1A C5A . . . . -118.2(3) ?
    C1B Fe C1A C5A . . . . 116.6(3) ?
    C4A Fe C1A C5A . . . . -37.2(2) ?
    C3B Fe C1A C5A . . . . -169.7(5) ?
    C3A Fe C1A C5A . . . . -80.7(3) ?
    C5B Fe C1A C2A . . . . -166.8(3) ?
    C4B Fe C1A C2A . . . . 162.7(5) ?
    C2B Fe C1A C2A . . . . -83.5(3) ?
    C5A Fe C1A C2A . . . . 118.2(3) ?
    C1B Fe C1A C2A . . . . -125.2(3) ?
    C4A Fe C1A C2A . . . . 81.0(3) ?
    C3B Fe C1A C2A . . . . -51.5(6) ?
    C3A Fe C1A C2A . . . . 37.6(3) ?
    C5B Fe C1A C5 . . . . -44.9(4) ?
    C4B Fe C1A C5 . . . . -75.3(7) ?
    C2B Fe C1A C5 . . . . 38.5(5) ?
    C5A Fe C1A C5 . . . . -119.8(5) ?
    C2A Fe C1A C5 . . . . 122.0(5) ?
    C1B Fe C1A C5 . . . . -3.2(4) ?
    C4A Fe C1A C5 . . . . -157.0(4) ?
    C3B Fe C1A C5 . . . . 70.4(7) ?
    C3A Fe C1A C5 . . . . 159.5(4) ?
    C5A C1A C2A C3A . . . .  -.4(5) ?
    C5 C1A C2A C3A . . . . 177.9(4) ?
    Fe C1A C2A C3A . . . . -59.7(3) ?
    C5A C1A C2A Fe . . . . 59.3(3) ?
    C5 C1A C2A Fe . . . . -122.3(4) ?
    C5B Fe C2A C3A . . . . 156.5(6) ?
    C4B Fe C2A C3A . . . . -46.1(6) ?
    C2B Fe C2A C3A . . . . -124.6(3) ?
    C1A Fe C2A C3A . . . . 119.2(4) ?
    C5A Fe C2A C3A . . . . 80.8(3) ?
    C1B Fe C2A C3A . . . . -166.6(3) ?
    C4A Fe C2A C3A . . . . 37.1(3) ?
    C3B Fe C2A C3A . . . . -81.7(3) ?
    C5B Fe C2A C1A . . . . 37.3(7) ?
    C4B Fe C2A C1A . . . . -165.2(4) ?
    C2B Fe C2A C1A . . . . 116.2(3) ?
    C5A Fe C2A C1A . . . . -38.4(2) ?
    C1B Fe C2A C1A . . . . 74.2(3) ?
    C4A Fe C2A C1A . . . . -82.1(3) ?
    C3B Fe C2A C1A . . . . 159.1(3) ?
    C3A Fe C2A C1A . . . . -119.2(4) ?
    C1A C2A C3A C4A . . . .  .7(5) ?
    Fe C2A C3A C4A . . . . -58.7(3) ?
    C1A C2A C3A Fe . . . . 59.3(3) ?
    C5B Fe C3A C4A . . . . -42.5(6) ?
    C4B Fe C3A C4A . . . . -79.3(3) ?
    C2B Fe C3A C4A . . . . -163.9(3) ?
    C1A Fe C3A C4A . . . . 81.9(3) ?
    C5A Fe C3A C4A . . . . 37.5(3) ?
    C2A Fe C3A C4A . . . . 120.1(4) ?
    C1B Fe C3A C4A . . . . 160.6(6) ?
    C3B Fe C3A C4A . . . . -122.1(3) ?
    C5B Fe C3A C2A . . . . -162.6(4) ?
    C4B Fe C3A C2A . . . . 160.6(3) ?
    C2B Fe C3A C2A . . . . 76.0(3) ?
    C1A Fe C3A C2A . . . . -38.2(3) ?
    C5A Fe C3A C2A . . . . -82.5(3) ?
    C1B Fe C3A C2A . . . . 40.5(8) ?
    C4A Fe C3A C2A . . . . -120.1(4) ?
    C3B Fe C3A C2A . . . . 117.8(3) ?
    C2A C3A C4A C5A . . . .  -.6(5) ?
    Fe C3A C4A C5A . . . . -59.1(3) ?
    C2A C3A C4A Fe . . . . 58.5(3) ?
    C5B Fe C4A C5A . . . . -79.4(3) ?
    C4B Fe C4A C5A . . . . -121.8(3) ?
    C2B Fe C4A C5A . . . . 167.9(6) ?
    C1A Fe C4A C5A . . . . 37.7(2) ?
    C2A Fe C4A C5A . . . . 82.3(3) ?
    C1B Fe C4A C5A . . . . -47.3(5) ?
    C3B Fe C4A C5A . . . . -162.5(3) ?
    C3A Fe C4A C5A . . . . 119.5(4) ?
    C5B Fe C4A C3A . . . . 161.1(3) ?
    C4B Fe C4A C3A . . . . 118.6(3) ?
    C2B Fe C4A C3A . . . . 48.3(8) ?
    C1A Fe C4A C3A . . . . -81.8(3) ?
    C5A Fe C4A C3A . . . . -119.5(4) ?
    C2A Fe C4A C3A . . . . -37.3(3) ?
    C1B Fe C4A C3A . . . . -166.8(4) ?
    C3B Fe C4A C3A . . . . 77.9(3) ?
    C3A C4A C5A C1A . . . .  .4(5) ?
    Fe C4A C5A C1A . . . . -59.1(3) ?
    C3A C4A C5A Fe . . . . 59.5(3) ?
    C2A C1A C5A C4A . . . .  .0(5) ?
    C5 C1A C5A C4A . . . . -178.4(4) ?
    Fe C1A C5A C4A . . . . 59.3(3) ?
    C2A C1A C5A Fe . . . . -59.3(3) ?
    C5 C1A C5A Fe . . . . 122.3(4) ?
    C5B Fe C5A C4A . . . . 117.3(3) ?
    C4B Fe C5A C4A . . . . 76.7(3) ?
    C2B Fe C5A C4A . . . . -171.1(5) ?
    C1A Fe C5A C4A . . . . -119.8(4) ?
    C2A Fe C5A C4A . . . . -81.2(3) ?
    C1B Fe C5A C4A . . . . 158.9(3) ?
    C3B Fe C5A C4A . . . . 48.2(7) ?
    C3A Fe C5A C4A . . . . -37.4(3) ?
    C5B Fe C5A C1A . . . . -122.9(3) ?
    C4B Fe C5A C1A . . . . -163.5(2) ?
    C2B Fe C5A C1A . . . . -51.3(6) ?
    C2A Fe C5A C1A . . . . 38.6(2) ?
    C1B Fe C5A C1A . . . . -81.3(3) ?
    C4A Fe C5A C1A . . . . 119.8(4) ?
    C3B Fe C5A C1A . . . . 168.0(6) ?
    C3A Fe C5A C1A . . . . 82.4(3) ?
    C5B Fe C1B C2B . . . . -119.5(4) ?
    C4B Fe C1B C2B . . . . -81.3(3) ?
    C1A Fe C1B C2B . . . . 119.0(3) ?
    C5A Fe C1B C2B . . . . 161.8(3) ?
    C2A Fe C1B C2B . . . . 77.3(4) ?
    C4A Fe C1B C2B . . . . -164.6(4) ?
    C3B Fe C1B C2B . . . . -37.6(3) ?
    C3A Fe C1B C2B . . . . 46.0(8) ?
    C4B Fe C1B C5B . . . . 38.2(3) ?
    C2B Fe C1B C5B . . . . 119.5(4) ?
    C1A Fe C1B C5B . . . . -121.5(3) ?
    C5A Fe C1B C5B . . . . -78.7(3) ?
    C2A Fe C1B C5B . . . . -163.2(3) ?
    C4A Fe C1B C5B . . . . -45.2(6) ?
    C3B Fe C1B C5B . . . . 81.9(3) ?
    C3A Fe C1B C5B . . . . 165.5(6) ?
    C5B C1B C2B C3B . . . .  .7(6) ?
    Fe C1B C2B C3B . . . . 59.5(4) ?
    C5B C1B C2B Fe . . . . -58.8(3) ?
    C5B Fe C2B C3B . . . . -81.7(3) ?
    C4B Fe C2B C3B . . . . -37.7(3) ?
    C1A Fe C2B C3B . . . . 161.7(3) ?
    C5A Fe C2B C3B . . . . -161.3(4) ?
    C2A Fe C2B C3B . . . . 117.7(3) ?
    C1B Fe C2B C3B . . . . -119.4(5) ?
    C4A Fe C2B C3B . . . . 38.5(8) ?
    C3A Fe C2B C3B . . . . 75.7(4) ?
    C5B Fe C2B C1B . . . . 37.7(3) ?
    C4B Fe C2B C1B . . . . 81.6(3) ?
    C1A Fe C2B C1B . . . . -78.9(3) ?
    C5A Fe C2B C1B . . . . -41.9(6) ?
    C2A Fe C2B C1B . . . . -122.9(3) ?
    C4A Fe C2B C1B . . . . 157.9(6) ?
    C3B Fe C2B C1B . . . . 119.4(5) ?
    C3A Fe C2B C1B . . . . -164.9(3) ?
    C1B C2B C3B C4B . . . .  .0(6) ?
    Fe C2B C3B C4B . . . . 59.3(4) ?
    C1B C2B C3B Fe . . . . -59.3(4) ?
    C5B Fe C3B C4B . . . . -37.4(3) ?
    C2B Fe C3B C4B . . . . -118.9(5) ?
    C1A Fe C3B C4B . . . . -163.0(4) ?
    C5A Fe C3B C4B . . . . 37.9(8) ?
    C2A Fe C3B C4B . . . . 159.3(3) ?
    C1B Fe C3B C4B . . . . -81.4(3) ?
    C4A Fe C3B C4B . . . . 74.2(4) ?
    C3A Fe C3B C4B . . . . 116.3(3) ?
    C5B Fe C3B C2B . . . . 81.5(4) ?
    C4B Fe C3B C2B . . . . 118.9(5) ?
    C1A Fe C3B C2B . . . . -44.1(7) ?
    C5A Fe C3B C2B . . . . 156.8(6) ?
    C2A Fe C3B C2B . . . . -81.8(4) ?
    C1B Fe C3B C2B . . . . 37.5(4) ?
    C4A Fe C3B C2B . . . . -166.9(3) ?
    C3A Fe C3B C2B . . . . -124.8(4) ?
    C2B C3B C4B C5B . . . .  -.6(6) ?
    Fe C3B C4B C5B . . . . 58.7(3) ?
    C2B C3B C4B Fe . . . . -59.3(4) ?
    C5B Fe C4B C3B . . . . 119.9(4) ?
    C2B Fe C4B C3B . . . . 37.9(3) ?
    C1A Fe C4B C3B . . . . 160.5(5) ?
    C5A Fe C4B C3B . . . . -166.0(3) ?
    C2A Fe C4B C3B . . . . -49.4(6) ?
    C1B Fe C4B C3B . . . . 81.6(4) ?
    C4A Fe C4B C3B . . . . -124.5(3) ?
    C3A Fe C4B C3B . . . . -82.8(4) ?
    C2B Fe C4B C5B . . . . -82.0(3) ?
    C1A Fe C4B C5B . . . . 40.6(6) ?
    C5A Fe C4B C5B . . . . 74.1(3) ?
    C2A Fe C4B C5B . . . . -169.3(4) ?
    C1B Fe C4B C5B . . . . -38.3(3) ?
    C4A Fe C4B C5B . . . . 115.6(3) ?
    C3B Fe C4B C5B . . . . -119.9(4) ?
    C3A Fe C4B C5B . . . . 157.3(3) ?
    C3B C4B C5B C1B . . . . 1.0(5) ?
    Fe C4B C5B C1B . . . . 60.4(3) ?
    C3B C4B C5B Fe . . . . -59.3(4) ?
    C2B C1B C5B C4B . . . . -1.0(5) ?
    Fe C1B C5B C4B . . . . -60.4(3) ?
    C2B C1B C5B Fe . . . . 59.4(4) ?
    C2B Fe C5B C4B . . . . 80.9(3) ?
    C1A Fe C5B C4B . . . . -164.8(3) ?
    C5A Fe C5B C4B . . . . -123.5(3) ?
    C2A Fe C5B C4B . . . . 166.6(5) ?
    C1B Fe C5B C4B . . . . 118.2(4) ?
    C4A Fe C5B C4B . . . . -81.9(3) ?
    C3B Fe C5B C4B . . . . 37.2(3) ?
    C3A Fe C5B C4B . . . . -51.8(6) ?
    C4B Fe C5B C1B . . . . -118.2(4) ?
    C2B Fe C5B C1B . . . . -37.4(3) ?
    C1A Fe C5B C1B . . . . 77.0(3) ?
    C5A Fe C5B C1B . . . . 118.2(3) ?
    C2A Fe C5B C1B . . . . 48.4(7) ?
    C4A Fe C5B C1B . . . . 159.8(3) ?
    C3B Fe C5B C1B . . . . -81.1(3) ?
    C3A Fe C5B C1B . . . . -170.0(4) ?
    C4 C5 C6 C7 . . . . -1.3(6) ?
    C1A C5 C6 C7 . . . . 177.9(4) ?
    C5 C6 C7 N8 . . . .  -.2(6) ?
    C5 C6 C7 C12 . . . . 178.5(4) ?
    C2 N1 N8 C7 . . . . -176.9(4) ?
    C2 N1 N8 C9 . . . .  -.4(4) ?
    C6 C7 N8 N1 . . . . 178.0(4) ?
    C12 C7 N8 N1 . . . .  -.9(6) ?
    C6 C7 N8 C9 . . . . 1.8(6) ?
    C12 C7 N8 C9 . . . . -177.1(4) ?
    C2 C3 C9 N8 . . . .  -.3(4) ?
    C2 C3 C9 C4 . . . . 178.2(5) ?
    N1 N8 C9 C3 . . . .  .5(4) ?
    C7 N8 C9 C3 . . . . 177.1(4) ?
    N1 N8 C9 C4 . . . . -178.3(3) ?
    C7 N8 C9 C4 . . . . -1.7(6) ?
    C5 C4 C9 C3 . . . . -178.3(5) ?
    C10 C4 C9 C3 . . . .  .9(7) ?
    C5 C4 C9 N8 . . . .  .1(6) ?
    C10 C4 C9 N8 . . . . 179.2(4) ?
    C5 C4 C10 N11 . . . . 177(5)    ?
    C9 C4 C10 N11 . . . . -2(5)    ?
    C6 C7 C12 C13 . . . . -7.2(6) ?
    N8 C7 C12 C13 . . . . 171.6(4) ?
    C7 C12 C13 N14 . . . . -161(8)    ?
